High-pressure vessel for growing group iii nitride crystals and method of growing group iii nitride crystals using high-pressure vessel and group iii nitride crystal

ABSTRACT

Present invention discloses a high-pressure vessel of large size formed with a limited size of e.g. Ni—Cr based precipitation hardenable superalloy. Vessel may have multiple zones. 
     For instance, the high-pressure vessel may be divided into at least three regions with flow-restricting devices and the crystallization region is set higher temperature than other regions. This structure helps to reliably seal both ends of the high-pressure vessel, at the same time, may help to greatly reduce unfavorable precipitation of group III nitride at the bottom of the vessel. 
     Invention also discloses novel procedures to grow crystals with improved purity, transparency and structural quality. Alkali metal-containing mineralizers are charged with minimum exposure to oxygen and moisture until the high-pressure vessel is filled with ammonia. Several methods to reduce oxygen contamination during the process steps are presented. Back etching of seed crystals and a new temperature ramping scheme to improve structural quality are disclosed.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of and claims priority toU.S. application Ser. No. 13/784,210, entitled “High-Pressure Vessel ForGrowing Group III Nitride Crystals And Method Of Growing Group IIINitride Crystals Using High-Pressure Vessel And Group III NitrideCrystal,” inventors Tadao Hashimoto, Edward Letts, and Masanori Ikari,filed Mar. 4, 2013, which is a continuation application of and claimspriority to U.S. application Ser. No. 13/491,392, entitled“High-Pressure Vessel For Growing Group III Nitride Crystals And MethodOf Growing Group III Nitride Crystals Using High-Pressure Vessel AndGroup III Nitride Crystal,” inventors Tadao Hashimoto, Edward Letts, andMasanori Ikari, filed Jun. 7, 2012, which is a divisional application ofand claims priority to U.S. application Ser. No. 12/455,683, entitled“High-Pressure Vessel For Growing Group III Nitride Crystals And MethodOf Growing Group III Nitride Crystals Using High-Pressure Vessel AndGroup III Nitride Crystal,” inventors Tadao Hashimoto, Edward Letts, andMasanori Ikari, filed Jun. 4, 2009, which claims priority to U.S. App.Ser. No. 61/058,910 entitled “High-Pressure Vessel For Growing Group IIINitride Crystals And Method Of Growing Group III Nitride Crystals UsingHigh-Pressure Vessel And Group III Nitride Crystal”, inventors TadaoHashimoto, Edward Letts, and Masanori Ikari, filed on Jun. 4, 2008, theentire contents of each of which are incorporated by reference herein asif put forth in full below. This application is also related to PCTapplication serial number PCT/US2009/046317 entitled “High-PressureVessel For Growing Group III Nitride Crystals And Method Of GrowingGroup III Nitride Crystals Using High-Pressure Vessel And Group IIINitride Crystal”, inventors Tadao Hashimoto, Edward Letts, and MasanoriIkari, filed on Jun. 4, 2009, the entire contents of which areincorporated by reference herein as if put forth in full below.

This application is also related to the following U.S. patentapplications:

PCT Utility Patent Application Serial No. US2005/024239, filed on Jul.8, 2005, by Kenji Fujito, Tadao Hashimoto and Shuji Nakamura, entitled“METHOD FOR GROWING GROUP III-NITRIDE CRYSTALS IN SUPERCRITICAL AMMONIAUSING AN AUTOCLAVE,” attorneys' docket number 30794.0129-WO-01(2005-339-1); U.S. Utility patent application Ser. No. 11/784,339, filedon Apr. 6, 2007, by Tadao Hashimoto, Makoto Saito, and Shuji Nakamura,entitled “METHOD FOR GROWING LARGE SURFACE AREA GALLIUM NITRIDE CRYSTALSIN SUPERCRITICAL AMMONIA AND LARGE SURFACE AREA GALLIUM NITRIDECRYSTALS,” attorneys docket number 30794.179-US-U1 (2006-204), whichapplication claims the benefit under 35 U.S.C. Section 119(e) of U.S.Provisional Patent Application Ser. No. 60/790,310, filed on Apr. 7,2006, by Tadao Hashimoto, Makoto Saito, and Shuji Nakamura, entitled “AMETHOD FOR GROWING LARGE SURFACE AREA GALLIUM NITRIDE CRYSTALS INSUPERCRITICAL AMMONIA AND LARGE SURFACE AREA GALLIUM NITRIDE CRYSTALS,”attorneys docket number 30794.179-US-P1 (2006-204);

U.S. Utility Patent Application Ser. No. 60/973,602, filed on Sep. 19,2007, by Tadao Hashimoto and Shuji Nakamura, entitled “GALLIUM NITRIDEBULK CRYSTALS AND THEIR GROWTH METHOD,” attorneys docket number30794.244-US-P1 (2007-809-1);

U.S. Utility patent application Ser. No. 11/977,661, filed on Oct. 25,2007, by Tadao Hashimoto, entitled “METHOD FOR GROWING GROUP III-NITRIDECRYSTALS IN A MIXTURE OF SUPERCRITICAL AMMONIA AND NITROGEN, AND GROUPIII-NITRIDE CRYSTALS GROWN THEREBY,” attorneys docket number30794.253-US-U1 (2007-774-2).

U.S. Utility Patent Application Ser. No. 61/067,117, filed on Feb. 25,2008, by Tadao Hashimoto, Edward Letts, Masanori Ikari, entitled “METHODFOR PRODUCING GROUP III-NITRIDE WAFERS AND GROUP III-NITRIDE WAFERS,”attorneys docket number 62158-30002.00.

all of which applications are incorporated by reference herein.

FIELD OF THE INVENTION

The invention is related to the high-pressure vessel used to grow groupIII nitride crystals expressed asB_(x)Al_(y)Ga_(z)In_(1-x-y-z)N(0≦x,y,z≦1) such as gallium nitride, boronnitride, indium nitride, aluminum nitride, and their solid solutions inhigh-pressure ammonia. The invention is also related to the method ofgrowing group III nitride crystals and the grown group III nitridecrystals.

BACKGROUND

(Note: This patent application refers to several publications andpatents as indicated with numbers within brackets, e.g., [x]. A list ofthese publications and patents can be found in the section entitled“References.”)

Gallium nitride (GaN) and its related group-III alloys are key materialsfor various opto-electronic and electronic devices such as lightemitting diodes (LEDs), laser diodes (LDs), microwave power transistors,and solar-blind photo detectors. Currently LEDs are widely used in cellphones, indicators, displays, and LDs are used in data storage diskdrives. However, the majority of these devices are grown epitaxially onheterogeneous substrates, such as sapphire and silicon carbide since GaNwafers are extremely expensive compared to these heteroepitaxialsubstrates. The heteroepitaxial growth of group III-nitride causeshighly defected or even cracked films, which hinders the realization ofhigh-end optical and electronic devices, such as high-brightness LEDsfor general lighting or high-power microwave transistors.

To solve fundamental problems caused by heteroepitaxy, it is useful toutilize single crystalline group III nitride wafers sliced from bulkgroup III nitride crystal ingots. For the majority of devices, singlecrystalline GaN wafers are favorable because it is relatively easy tocontrol the conductivity of the wafer and GaN wafer will provide thesmallest lattice/thermal mismatch with device layers. However, due tothe high melting point and high nitrogen vapor pressure at elevatedtemperature, it has been difficult to grow GaN crystal ingots. Growthmethods using molten Ga, such as high-pressure high-temperaturesynthesis [1,2] and sodium flux [3,4], have been proposed to grow GaNcrystals, nevertheless the crystal shape grown in molten Ga becomes athin platelet because molten Ga has low solubility of nitrogen and a lowdiffusion coefficient of nitrogen.

The ammonothermal method, which is a solvothermal method usinghigh-pressure ammonia as a solvent has demonstrated successful growth ofreal bulk GaN [5-10]. This new technique is able to grow large GaNcrystal ingots, because high-pressure ammonia used as a fluid medium hasa high solubility of source materials such as GaN polycrystals ormetallic Ga, and high transport speed of dissolved precursors can beachieved. There are mainly three approaches to grow GaN in supercriticalammonia; a method using ammonobasic solutions in single reactor withexternal heating as disclosed in [6-10] and a method using ammonoacidicsolutions in Pt-lined single reactor with external heating as disclosedin [1,1] and a method using supercritical ammonia with a capsule andinternal heaters enclosed in high-pressure reactor as disclosed in[1,2]. The latter two methods have disadvantages in expanding thereactor scale. For the ammonoacidic approach, it is extremely expensiveto use a Pt-liner in a large-scaled pressure vessel. As for the internalcapsule, it is structurally very challenging to operate the capsulereactor larger than 2″ diameter. Therefore, the ammonothermal growthusing basic mineralizer is the most practical approach to mass-producebulk GaN. As disclosed in the literature [6, 13-16], GaN has retrogradesolubility in supercritical ammonobasic solutions. Therefore, in theconventional ammonothermal growth using basic mineralizer, thetemperature for a nutrient zone is set lower than that for acrystallization zone. In addition to this temperature setting, basicammonothermal method differs in many aspects from other solvothermalmethods such as hydrothermal growth of quartz and zinc oxide. Because ofthis difference, it is not straightforward to apply the solvothermalmethod to grow group III nitride crystals and more improvements arerequired to realize mass production of GaN wafers by the ammonothermalmethod.

First, state-of-the-art ammonothermal method [6-10] lacks scalabilityinto industrial production because it is quite difficult to obtain largeenough superalloy material to construct a high-pressure vessel. Sincegroup III nitrides have high melting temperature or dissociationtemperature, crystal growth requires relatively higher temperature thanother materials grown by the solvothermal method. For example, bothquartz and zinc oxide (ZnO) are grown at about 300-400° C. by thehydrothermal method. On the other hand, typical growth temperature ofGaN in the ammonothermal method is 450-600° C. [6-10]. Furthermore, ourexperiment showed that growth at 550° C. or above is typically needed toobtain high-quality crystals. Therefore, Ni—Cr based precipitationhardenable (or age hardenable) superalloy such as Rene-41 (Haynes R-41or Pyromet 41), Inconel 720 (Pyromet 720), Inconel 718 (Pyromet 718),and Waspaloy A must be used for a vessel material. These superalloys areforged to obtain small-sized, dense grain structure which provides thenecessary tensile strength for conditions allowing the solvent to besupercritical. However, if the solid dimension of the piece being worked(such as its thickness) becomes too large, the grain structure necessaryfor high-tensile strength cannot be obtained by forging. This is becausethe forging pressure is always applied from the surface during theforging process and the grain size at the inner portion of the materialtends to be unaffected if the work size exceeds a certain size. Crackingduring the forging/cooling process is also profound for large diameterrods. These problems limit the available size of Ni—Cr basedprecipitation hardenable superalloys. In case of Rene-41, the maximumavailable outer diameter for a rod is 12 inch, although the maximumouter diameter for an as-cast (i.e. unforged) rod is larger than 12inch.

Another obstacle to apply the ammonothermal method to commercialproduction of GaN single crystals is mediocre quality of grown crystals.Currently, their purity, transparency and structural quality are notsufficient for commercial use. In particular, oxygen concentration is atthe order of 10²⁰ cm⁻³. This high level of oxygen together with Gavacancy is thought to be the origin of brownish color of GaN grown bythe ammonothermal method. The grown crystals also show multiple grainsin the growth plane.

Considering above-mentioned limitations, this patent discloses severalnew ideas to realize a high-pressure vessel that is practically usablefor production of group III nitride crystals by the ammonothermalmethod. This patent also discloses new ways to improve purity,transparency, and structural quality of group III nitride crystals grownby the ammonothermal method.

SUMMARY OF THE INVENTION

The present invention discloses a new high-pressure vessel suitable foruse in ammonothermal growth of a Group III-nitride material. The vesselis made from a raw material such as superalloy rod or billet limited insize today when incorporated into a high-pressure vessel. Amultiple-zone high-pressure vessel, which can attain the largestpossible high-pressure vessel is disclosed.

The vessel may have one or more clamps to seal the vessel. A clamp maybe formed of a metal or alloy having grain flow in a radial direction inthe clamp. This configuration enables the vessel to be much greater insize than vessels today.

The high-pressure vessel may be divided into at least three regions byflow-restricting devices such as baffles. In this embodiment, the vesselhas a nutrient region in which a nutrient such as polycrystalline GaN orother feed material is dissolved or supplied. The vessel also has acrystallization region in which the group III-nitride material iscrystallized upon a seed material. The vessel also has a buffer regionbetween the nutrient region and the crystallization region, one or morecool zones adjacent to the crystallization zone and/or the nutrient zoneand in the vicinity of a clamp, or both.

This invention also discloses new procedures to grow crystals withimproved purity, transparency and structural quality. Alkalimetal-containing mineralizers are charged with minimum exposure tooxygen and moisture until the high-pressure vessel is filled withammonia. Several methods to reduce oxygen contamination during theprocess steps are presented. Also, back etching of seed crystals and anew temperature ramping scheme to improve structural quality aredisclosed.

In addition, the current invention discloses a method of reducingparasitic deposition of polycrystalline GaN on the inner surface of thepressure vessel while optionally improving structural quality andwithout reducing growth rate. Because of the retrograde solubility ofGaN in the ammonothermal growth using basic mineralizers, thetemperature in the crystallization region is conventionally set higherthan the temperature in the nutrient region. We, however, discoveredthat GaN can be grown by setting the temperature of the crystallizationregion slightly lower than the temperature of the nutrient region. Byutilizing this “reverse” temperature setting for growth, parasiticdeposition of GaN on the reactor wall was greatly reduced. Moreover, thestructural quality of grown crystal was improved without sacrificinggrowth rate.

BRIEF DESCRIPTION OF THE DRAWINGS

The patent or application file contains at least one drawing executed incolor. Copies of this patent or patent application publication withcolor drawing(s) will be provided by the Office upon request and paymentof the necessary fee.

Referring now to the drawings in which like reference numbers representcorresponding parts throughout:

FIG. 1 is a schematic drawing of the high-pressure vessel in thisinvention.

In the figure each number represents the followings:

-   -   1. High-pressure vessel    -   2. Lid    -   3. Clamp    -   4. Gasket    -   5. Heater(s) for the crystallization region    -   6. Heater(s) for the dissolution region    -   7. Flow-restricting baffle(s)    -   8. Nutrient basket    -   9. Nutrient    -   10. Seed crystals    -   11. Flow-restricting baffle(s)    -   12. Blast containment enclosure    -   13. Valve    -   14. Exhaust tube    -   15. Device to operate valve

FIG. 2 is a photograph comparing colorations depending on mineralizersand additives.

FIG. 3 is a photograph of GaN crystal with Mg additive.

DETAILED DESCRIPTION OF THE INVENTION Overview

The present invention provides a design to achieve a high-pressurevessel suitable for mass production of group III-nitride crystals by theammonothermal method. With the limited size of available Ni—Cr basedprecipitation hardenable superalloy, innovative designs are presented tomaximize the vessel size. Also, methods of growing improved-qualitygroup III nitride crystals are presented.

In one instance, the invention provides a reactor for ammonothermalgrowth of a group III-nitride crystalline ingot. The reactor has: a bodydefining a chamber; and a first clamp for sealing an end of the reactor,wherein the first clamp is formed of a metal or alloy having a grainflow in a radial direction in the clamp.

In another instance, a reactor for ammonothermal growth of a groupIII-nitride crystalline ingot has: a body defining a chamber; a firstheater for heating a nutrient region of the reactor; a second heater forheating a crystallization region of the reactor; a third region selectedfrom a buffer region and an end region; and at least one baffleseparating the crystallization region from the nutrient region or thecrystallization region from an end region of the reactor, with thequalifications that the buffer region when present is defined by aplurality of baffles comprising a first end baffle and an opposite endbaffle with one or more optional baffles therebetween, and a distancefrom the first end baffle to the opposite end baffle of the plurality isat least ⅕ of an inner diameter of the reactor; and the reactor furthercomprises a first clamp at the end region when the end region ispresent.

Any of the reactors described herein may have a single opening at anend. Alternatively, any of the reactors described herein may have two ormore openings, with one opening at each end of the reactor body. Thereactor may be generally cylindrical, or the reactor may be formed inanother shape such as spherical or semispherical.

A reactor as discussed herein may have a buffer region and/or one ormore cooled end regions.

A clamp for the reactor, such as a clamp positioned in an end region,may be formed of a metal or alloy having a grain flow in a radialdirection in the clamp. The clamp may be formed of a superalloy such asa Ni—Cr superalloy. Alternatively, a clamp may be formed of highstrength steel.

A reactor may have a first heater that is configured to maintain thenutrient region of the reactor at a temperature near but greater than atemperature of the reactor in a crystallization region of the reactorwhen the reactor is configured to grow a gallium nitride crystal havingretrograde solubility in supercritical ammonia.

The reactor may be configured so that the first heater maintains thenutrient region no more than about 20° C. greater than the temperatureof the crystallization region.

Any reactor may have a second clamp for sealing a second end of thereactor. The second clamp may be identical to the first clamp discussedabove.

The clamp may be formed in two or three or more pieces so that the clampcan be disassembled and removed from the reactor. The pieces may be heldtogether by bolts formed of the same material as the clamps.

A reactor for ammonothermal growth of a group III-nitride crystallineingot may also have a body defining a chamber; and a mineralizer in anencapsulant, wherein the encapsulant is an oxygen- and water-impermeablematerial capable of rupturing under growth conditions in the reactor.

As discussed in further detail below, the encapsulant may be a metal oralloy coating on the mineralizer that softens or melts at crystal growthconditions in the reactor.

The encapsulant may instead or additionally comprise a water- andoxygen-impermeable container that ruptures under crystal growthconditions in the reactor.

The container may have a chamber which contains the encapsulant and hasa pressure much less than a pressure within the reactor under crystalgrowth conditions, so that the pressure on the container exceeds itsyield strength when the reactor attains operating pressure andtemperature.

Any of the reactors disclosed herein may operate using an ammonobasicsupercritical solution or an ammonoacidic supercritical solution. Themineralizer may therefore be basic or acidic. Such mineralizers arewell-known in the art.

Also disclosed herein is a method of forming a group III-nitridecrystalline material. The method includes:

providing a mineralizer substantially free of oxygen and water to areaction chamber of an ammonothermal growth reactor

evacuating the chamber

growing the group III-nitride crystalline material in the chamber.

Any method disclosed herein may include providing an oxygen getter inthe reaction chamber.

A method of forming gallium nitride crystalline material may comprise

heating a nutrient comprising polycrystalline GaN in a nutrient regionof a reactor

heating a seed material in a crystallization region of the reactor

dissolving the polycrystalline GaN in supercritical ammonia

depositing the dissolved GaN on the seed material to grow the galliumnitride crystalline material

wherein the temperature of the nutrient region is greater than but nearthe temperature of the crystallization region.

In such a method, the difference in temperature between the nutrientregion and the crystallization region may be no more than about 50, 40,30, 25, 20, 15, or 10° C. during the act of depositing the dissolved GaNon the seed material.

Any method discussed herein may further comprise back-etching thenutrient prior to the act of growing the crystalline material.

Reactors and methods are discussed in greater detail below.

Technical Description

Since there is a size limitation in forged materials, it is not possibletoday to obtain large diameter rod of various metals or alloys such asprecipitation hardenable Ni—Cr based superalloy from which a pressurevessel suitable for ammonothermal growth of a group III-nitridecrystalline material can be made. For example, the maximum diameter ofas-cast R-41 billet is 17 inches, and this billet is forged (e.g.round-forged, where the forging pressure is applied along the radialdirection) into 12-inch diameter rod before making the reactor. This isthe maximum diameter of forged rod in state-of-the-art technology andmeans that the maximum outer diameter of the high-pressure vessel can beclose to 12 inches. However, this maximum diameter cannot be realizedusing existing methods because it is also necessary to form clamps forthe high-pressure vessel from the forged metal or alloy.

For a high-pressure vessel of this scale, a clamp-type closure is saferand more practical due to the increased cover load (i.e. the forceapplied to lids at the conditions present in ammonothermal crystalgrowth). A screw-type closure is not practical for a high-pressurevessel having an inner diameter larger than 2 inches because the screwcap requires too many threads to hold the cover load.

However, since the clamp diameter must be larger than the outer diameterof the high-pressure vessel, the maximum outer diameter of thehigh-pressure vessel is limited by the clamp diameter. Using R-41 forexample, the clamp diameter of 12 inch results in a high-pressure vesselwith 4-6 inch outer diameter and 2-3 inch inner diameter. Although onecan produce 2-inch wafers of GaN with such high-pressure vessel, theproductivity is not large enough to compete with other growth methodssuch as hydride vapor phase epitaxy (HVPE).

Example 1

To solve the above-mentioned problem, a few methods to obtain largerclamps were sought and we discovered it possible to manufacture a largediameter disk with e.g. precipitation hardenable Ni—Cr based superalloyor other metal or alloy by forging as-cast billet along longitudinaldirection. With this method, a 17-inch as-cast billet is forged alongthe longitudinal direction to form a 20-inch diameter, 1-foot thickdisk. The forging process usually creates a directional microstructure(grain flow) which determines tensile strength of the material.

The grain flow of the round rod to construct the body and lids istypically along the longitudinal direction whereas the grain flow of thedisks to construct the clamps is along the radial direction. While onemight expect a disk with radial grain flow rather than axial grain flowto not have sufficient tensile strength to reliably clamp a lid to areactor body during use, this difference does not have a significantimpact on the reliability of the high-pressure vessel as long as thehigh-pressure vessel is designed with sufficient safety factor. Withthis method, we designed a high-pressure vessel with 11.5″ outerdiameter, 4.75″ inner diameter, and height larger than 47.5″. Since theheight of the high-pressure vessel is large, it is necessary to bore ahole from both ends to form a chamber within the reactor vessel.Therefore a high-pressure vessel might require two lids, one on eachend. The clamp diameter in this instance is 20″ and the thickness is12″, which ensures sufficient strength to hold a lid during crystalgrowth. A large clamp such as this may be formed of two or more clampsections that are e.g. bolted together to form the finished clamp.

A large reactor such as the one discussed above provides greateropportunities to improve the quality of larger-diameter crystal grown inthe reactor. Hot ammonia circulates inside the high-pressure vessel andtransfers heat. To establish preferable temperature distribution,flow-restricting baffles may be used. Unlike the conventionalammonothermal reactor, the invented high-pressure vessel may be equippedwith a flow restricting baffle to cool the bottom region (11 in FIG. 1).In this way, the temperature around the seal and the clamp is maintainedlower than that of the crystallization region to improve reliability. Inaddition, this temperature distribution prevents unnecessaryprecipitation of GaN on the bottom lid.

The large reactor design also allows a large buffer region to beincorporated between the crystallization region and the nutrient region.This buffer region may comprise multiple baffles where holes or openingsin a baffle are offset from holes or openings in adjacent baffles.

These baffles increase the average residence time within the bufferregion while providing some regions of relatively stagnant flow andother regions of vortex flow for ammonia passing through the regionsbetween baffles. The average flow-rate from the nutrient region to thecrystallization region in the larger-diameter reactor may also be lessthan the average flow-rate from the nutrient region to thecrystallization region in a smaller-diameter reactor.

The buffer region may also be positioned primarily or exclusivelyadjacent to the heaters for the nutrient region for a reactor configuredto provide a lower temperature in the nutrient region and highertemperature in the crystallization region to take advantage of theretrograde solubility of e.g. GaN in supercritical ammonia. Or, thebuffer region may extend past heaters for the crystallization zone toprovide earlier heating or cooling of the supercritical ammonia, so thatthe ammonia solution is more likely to be at the desired temperaturewhen the solution encounters the seed material.

The slower ammonia flow supplied in the crystallization region with itsincreased residence time in the buffer zone, of the supersaturatedammonia, may thus increase the growth rate as shown in Example 3.

As the size of the high-pressure vessel increases, the total internalvolume becomes large. Thus, it is important to mitigate possible blasthazards. The equivalent blast energy in this example is estimated to beas high as 9 lbs TNT. In this example, we designed a blast containmentenclosure having ½ inch-thick steel wall (12 in FIG. 1). One importantthing is that the ammonia in the high-pressure vessel can be released byremote operation of the high-pressure valve (13 in FIG. 1). The valvecan be remote-operated via either mechanical, electrical, or pneumaticway.

Example 2

Another method to realize a large diameter high-pressure vessel is touse high-strength steel for the clamp material. Although the maximumpractical temperature for high-strength steel (such as 4140) is 550° C.,the maximum available size is large enough to fabricate clamps forhigh-pressure vessel having 12-inch outer diameter. In this case extracaution is necessary to control the clamp temperature. An end region inthe reactor that has one or more baffles to impede ammonia flow permitsammonia to cool in an end region, reducing the reactor temperature inthat region and allowing a clamp to be formed of a material such as highstrength steel that might not otherwise be used to form a clamp. Also,appropriate anti-corrosion coating is advisable in case of ammonia leaksince steel is susceptible to corrosion by basic ammonia.

Example 3

In this example, a high-pressure vessel having an inner diameter of 1inch was used to demonstrate the enhanced growth rate by having one ormore buffer regions between the crystallization region and the nutrientregion. Unlike the Examples 1, 2, this high-pressure vessel has an openend on one side only. The chamber of the high-pressure vessel is dividedinto several regions. From bottom to top, there were a crystallizationregion, buffer regions, and a nutrient region. GaN crystals were grownwith 2 buffer regions, 5 buffer regions, and 8 buffer regions and thegrowth rate in each condition was compared. First, the high-pressurevessel was loaded with 4 g of NaNH₂, a seed crystal suspended from aflow-restricting baffle having 55 mm-long legs (the first baffle). Tocreate buffer regions, 2 flow restricting baffles with 18 mm legs, 5flow restricting baffles with 18 mm legs or 8 flow restricting baffleswith 10 mm legs were set on top of the first baffle (i.e. buffer regionswith height of 18 mm were created for the first two conditions andbuffer regions with height of 10 mm were created for the lastcondition). All of the baffles had ¼″ hole at the center and the totalopening was about 14%. The baffle holes in this instance were not offsetfrom one another. On top of these baffles, a Ni basket containing 10 gof polycrystalline GaN was placed and the high-pressure vessel wassealed with a lid. All of these loading steps were carried out in aglove box filled with nitrogen. The oxygen and moisture concentration inthe glove box was maintained to be less than 1 ppm. Then, thehigh-pressure vessel was connected to a gas/vacuum system, which canpump down the vessel as well as supply NH₃ to the vessel. First, thehigh-pressure vessel was pumped down with a turbo molecular pump toachieve pressure less than 1×10⁻⁵ mbar.

The actual pressure in this example was 2.0×10⁻⁶, 2.4×10⁻⁶ and 1.4×10⁻⁶mbar for conditions with 2, 5, and 8 buffer regions, respectively. Inthis way, residual oxygen and moisture on the inner wall of thehigh-pressure vessel were removed. After this, the high-pressure vesselwas chilled with liquid nitrogen and NH₃ was condensed in thehigh-pressure vessel. About 40 g of NH₃ was charged in the high-pressurevessel. After closing the high-pressure valve of the high-pressurevessel, the vessel was transferred to a two zone furnace. Thehigh-pressure vessel was heated to 575° C. of the crystallization zoneand 510° C. for the nutrient zone. After 7 days, ammonia was releasedand the high-pressure vessel was opened. The growth rate for conditionswith 2, 5, and 8 buffer regions were 65, 131, and 153 microns per day,respectively. The growth rate was increased with increased number ofbuffer regions between the crystallization region and the nutrientregion. One reason for the enhanced growth rate is that the convectiveflow of ammonia became slower as the buffer regions increased. Anotherreason is creating larger temperature difference by restricting heatexchange between the nutrient region and crystallization region.Therefore, adjusting the opening of the baffle, changing the position ofholes on the baffle, adjusting the height of the buffer region isexpected to have a similar effect on growth rate. To enhance the growthrate effectively, it is desirable to maintain the height of the bufferregion larger than ⅕ of the inner diameter of the high-pressure vesselso that enough space is created to promote stagnant/vortex flow ofammonia.

Additional Technical Description

Here several methods to improve purity, transparency, and structuralquality of GaN grown by the ammonothermal method are presented. Thefollowings examples help illustrate further principles of the claimedinvention, as do the preceding examples.

Example 4

In this example, a high-pressure vessel having an inner diameter of 1inch was used to demonstrate the ammonothermal growth steps withhigh-vacuum pumping before ammonia filling. Unlike the Examples 1, 2,this high-pressure vessel has an open end on one side only. Allnecessary sources and internal components including 10 g ofpolycrystalline GaN nutrient held in a Ni basket, 0.3 mm-thick singlecrystalline GaN seeds, and three flow-restricting baffles were loadedinto a glove box together with the high-pressure vessel. The glove boxis filled with nitrogen and the oxygen and moisture concentration ismaintained to be less than 1 ppm. Since the mineralizers are reactivewith oxygen and moisture, the mineralizers are stored in the glove boxat all times. 4 g of NaNH₂ was used as a mineralizer. After loading themineralizer into the high-pressure vessel, three baffles together withseeds and nutrient were loaded. After sealing the high-pressure vessel,it was taken out of the glove box. Then, the high-pressure vessel wasconnected to a gas/vacuum system, which can pump down the vessel as wellas supply NH₃ to the vessel. The high-pressure vessel was heated at 110°C. and evacuated with a turbo molecular pump to achieve pressure lessthan 1×10⁻⁵ mbar. The actual pressure before filling ammonia was2.0×10⁻⁶ mbar. In this way, residual oxygen and moisture on the innerwall of the high-pressure vessel were removed. After this, thehigh-pressure vessel was chilled with liquid nitrogen and NH₃ wascondensed in the high-pressure vessel. Approximately 40 g of NH₃ wascharged in the high-pressure vessel. After closing the high-pressurevalve of the high-pressure vessel, it was transferred to a two zonefurnace. The high-pressure vessel was heated up. The crystallizationregion was maintained at 575° C. and the nutrient region was maintainedat 510° C. After 7 days, ammonia was released and the high-pressurevessel was opened. The grown crystals showed dark brownish color (thetop sample in FIG. 2) and the oxygen concentration measured withsecondary ion mass spectroscopy (SIMS) was 1.2-2.8×10²⁰ cm⁻³. In thisexample, pumping and heating of the high-pressure vessel did notcontribute to oxygen reduction. This is because the NaNH₂ mineralizercontained significant amount of oxygen/moisture as shown in the nextexample. After minimizing oxygen/moisture content of mineralizers,pumping and heating of the high-pressure vessel is necessary to minimizepossible source of oxygen in the process.

Example 5

In this example, a high-pressure vessel having an inner diameter of 1inch was used to demonstrate the ammonothermal growth steps using Namineralizer with high-vacuum pumping before ammonia filling. Unlike theExamples 1, 2, this high-pressure vessel has an open end on one side.All necessary sources and internal components including 10 g ofpolycrystalline GaN nutrient held in a Ni basket, 0.3 mm-thick singlecrystalline GaN seeds, and six flow-restricting baffles were loaded intoa glove box together with the high-pressure vessel. The glove box isfilled with nitrogen and the oxygen and moisture concentration ismaintained to be less than 1 ppm. Since the mineralizers are reactivewith oxygen and moisture, the mineralizers are stored in the glove boxat all times. 2.3 g of Na cube was used as a mineralizer. The surface ofthe Na was “peeled” to remove oxide layer. However, even in theglovebox, the fresh surface changed color in seconds, which representedinstantaneous oxidation of the Na surface. After loading the mineralizerinto the high-pressure vessel, six baffles together with seeds andnutrient were loaded. After sealing the high-pressure vessel, it wastaken out of the glove box. Then, the high-pressure vessel was connectedto a gas/vacuum system, which can pump down the vessel as well as supplyNH₃ to the vessel. The high-pressure vessel was evacuated at roomtemperature with a turbo molecular pump to achieve pressure less than1×10⁻⁵ mbar. The actual pressure before filling ammonia was 1.5×10⁻⁶mbar. In this way, residual oxygen and moisture on the inner wall of thehigh-pressure vessel were removed. After this, the high-pressure vesselwas chilled with liquid nitrogen and NH₃ was condensed in thehigh-pressure vessel. Approximately 40 g of NH₃ was charged in thehigh-pressure vessel. After closing the high-pressure valve of thehigh-pressure vessel, it was transferred to a two zone furnace. Thehigh-pressure vessel was heated up. The crystallization region wasmaintained at 575° C. and the nutrient region was maintained at 510° C.After 7 days, ammonia was released and the high-pressure vessel wasopened. The coloration of the grown crystals was improved (the secondsample from the top in FIG. 2). The oxygen concentration measured bysecondary ion mass spectroscopy (SIMS) was 0.7-2.0×10¹⁹ cm⁻³, which wasmore than one order of magnitude lower level than the sample in Example4. Using mineralizer with low oxygen/moisture content together withpumping the high-pressure vessel is shown to be important to minimizeoxygen concentration in the crystal.

Example 6

As shown in Example 5, reducing oxygen/moisture content of mineralizersis vital for improving purity of GaN. As explained in Example 5, Nasurface was oxidized quickly even in the glove box. Therefore, it isimportant to reduce exposed surface of Na or alkali metal mineralizers.Oxidation of Na was reduced by melting the Na in Ni crucible. A hotplate was introduced in the glovebox mentioned in the Example 5 to heatNi crucible under oxygen and moisture controlled environment. Afterremoving surface oxide layer of Na, it was placed in a Ni crucibleheated on the hot plate. When the Na melts, its surface fully contactson the bottom and wall of the crucible. Ni foil is placed on the topsurface of the Na to minimize exposed surface of Na. Since the Nicrucible is small enough to fit the autoclave and Ni is stable in thegrowth environment, the Ni crucible containing Na can be loaded in thehigh-pressure vessel directly. In this way, most of surface of Na iscovered with Ni, therefore oxidation of Na is minimized. Any metal whichis stable in the supercritical ammonia can be used for cruciblematerial. Typical metal includes Ni, V, Mo, Ni—Cr superalloy, etc.

Example 7

Another method to cover fresh surfaces of alkali metal is to punchthrough alkali metal cake with hollow metal tubing. This way, thesidewall of the alkali metal is automatically covered with the innerwall of the tubing, thus reduces surface area exposed to theenvironment. For example, a slab-shaped Na sandwiched with Ni foil canbe prepared by attaching Ni foil immediately after cutting top or bottomsurface of the slab. Although the sidewall of the slab is not covered,punching through the Na slab with Ni tubing can create Na cake withsidewall attaching to Ni and top and bottom surface covered with Nifoil. In this way, oxygen/moisture content of alkali metal mineralizercan be greatly reduced.

Example 8

When the high-pressure vessel becomes large, it is impossible to loadmineralizers to the high-pressure vessel in a glove box. Therefore it isnecessary to take alternative procedure to avoid exposure ofmineralizers to oxygen/moisture. One method is to use an airtightcontainer which cracks under high pressure. Here is one example of theprocedure. Mineralizer is loaded into the airtight container in theglove box. If alkali metal is used, it can be melted and solidified inthe way explained in Example 6. Then, the high pressure vessel is loadedwith the airtight container and all other necessary parts and materialsunder atmosphere. After sealing the high-pressure vessel, it is pumpeddown and heated to evacuate residual oxygen/moisture. Ammonia is chargedin the high-pressure vessel and the high-pressure vessel is heated togrow crystals. When internal ammonia pressure exceeds cracking pressureof the airtight container, the mineralizer is released into the ammonia.In this way, mineralizers can be added to ammonia without exposing themto oxygen and moisture.

Example 9

To further reduce oxygen concentration, it is effective to remove oxygenin the high-pressure vessel after the high-pressure vessel is sealed andbefore the ammonia is charged. One practical procedure is to pump andbackfill reducing gas in the high-pressure vessel. The reducing gas suchas ammonia and hydrogen reacts with residual oxygen in the high-pressurevessel and form water vapor. Therefore, it is further effective to heatthe high-pressure vessel to enhance the reduction process.

Example 10

In this example, a high-pressure vessel having an inner diameter of 1inch was used to demonstrate the ammonothermal growth steps with Ceaddition as an oxygen getter. Unlike the Examples 1, 2, thishigh-pressure vessel has an open end on one side. All necessary sourcesand internal components including 5 g of polycrystalline GaN nutrientheld in a Ni basket, 0.4 mm-thick single crystalline GaN seeds, and sixflow-restricting baffles were loaded into a glove box together with thehigh-pressure vessel. The glove box is filled with nitrogen and theoxygen and moisture concentration is maintained to be less than 1 ppm.Since the mineralizers are reactive with oxygen and moisture, themineralizers are stored in the glove box at all times. 2.4 g of Na wasused as a mineralizer. After loading the mineralizer into thehigh-pressure vessel, six baffles together with seeds and nutrient wereloaded. Then, 0.4 g of Ce powder was added. After sealing thehigh-pressure vessel, it was taken out of the glove box. Thehigh-pressure vessel was connected to a gas/vacuum system, which canpump down the vessel as well as supply NH₃ to the vessel. Thehigh-pressure vessel was evacuated with a turbo molecular pump toachieve pressure less than 1×10⁻⁵ mbar. The actual pressure beforefilling ammonia was 2.6×10⁻⁶ mbar. In this way, residual oxygen andmoisture on the inner wall of the high-pressure vessel were removed.After this, the high-pressure vessel was chilled with liquid nitrogenand NH₃ was condensed in the high-pressure vessel. Approximately 40 g ofNH₃ was charged in the high-pressure vessel. After closing thehigh-pressure valve of the high-pressure vessel, it was transferred to atwo zone furnace. The high-pressure vessel was heated up. First, thefurnace for the crystallization region was maintained at 510° C. and thenutrient region was maintained at 550° C. for 24 hours. This reversetemperature setting was discovered to be beneficial for improvingcrystal quality as shown in Example 15. Then, the temperatures for thecrystallization region and the nutrient region were set to 575 and 510°C. for growth. After 4 days, ammonia was released and the high-pressurevessel was opened. The grown crystal showed yellowish color (the middlesample in FIG. 2), which represented improvement of transparency.

When 0.1 g of Ca lump was added instead of Ce, the grown crystal wassemi transparent with slight tan color (the bottom sample in FIG. 2),which represented improvement of transparency. Similar result can beexpected with adding oxygen getter containing Al, Mn, or Fe.

Example 11

In this example, a high-pressure vessel having an inner diameter of 1inch was used to demonstrate the ammonothermal growth steps with Baddition as surfactant. Unlike the Examples 1, 2, this high-pressurevessel has an open end on one side. All necessary sources and internalcomponents including 5 g of polycrystalline GaN nutrient held in a Nibasket, one 0.4 mm-thick single crystalline GaN seed, and sixflow-restricting baffles were loaded into a glove box together with thehigh-pressure vessel. The glove box is filled with nitrogen and theoxygen and moisture concentration is maintained to be less than 1 ppm.Since the mineralizers are reactive with oxygen and moisture, themineralizers are stored in the glove box at all times. 2.4 g of Na wasused as a mineralizer. After loading the mineralizer into thehigh-pressure vessel, six baffles together with the seed and nutrientwere loaded. Then, 0.1 g of BN platelet was added. After sealing thehigh-pressure vessel, it was taken out of the glove box. Thehigh-pressure vessel was connected to a gas/vacuum system, which canpump down the vessel as well as supply NH₃ to the vessel. Thehigh-pressure vessel was evacuated with a turbo molecular pump toachieve pressure less than 1×10⁻⁵ mbar. The actual pressure beforefilling ammonia was 1.8×10⁻⁶ mbar. In this way, residual oxygen andmoisture on the inner wall of the high-pressure vessel were removed.After this, the high-pressure vessel was chilled with liquid nitrogenand NH₃ was condensed in the high-pressure vessel. Approximately 40 g ofNH₃ was charged in the high-pressure vessel. After closing thehigh-pressure valve of the high-pressure vessel, it was transferred to atwo zone furnace. The high-pressure vessel was heated up. First, thefurnace for the crystallization region was maintained at 510° C. and thenutrient region was maintained at 550° C. for 24 hours. This reversetemperature setting was discovered to be beneficial for improvingcrystal quality as shown in Example 15. Then, the temperatures for thecrystallization region and the nutrient region were set to 575 and 510°C. for growth. After 4 days, ammonia was released and the high-pressurevessel was opened. The grown crystal showed less brownish color (thesecond sample from the bottom in FIG. 2), which showed improvement oftransparency. Also, the structural quality was improved compared to onewith conventional ammonothermal growth [5]. The full width half maximum(FWHM) of X-ray rocking curve from (002) and (201) planes were 295 and103 arcsec, respectively. These numbers are about 5 times smaller thancrystals reported in reference [5]. Similar result can be expected withadding surfactant containing In, Zn, Sn, or Bi.

Example 12

In this example, a high-pressure vessel having an inner diameter of 1inch was used to demonstrate the ammonothermal growth steps with Mgaddition as an oxygen getter. Unlike the Examples 1, 2, thishigh-pressure vessel has an open end on one side. All necessary sourcesand internal components including 5 g of polycrystalline GaN nutrientheld in a Ni basket, 0.4 mm-thick single crystalline GaN seeds, and sixflow-restricting baffles were loaded into a glove box together with thehigh-pressure vessel. The glove box is filled with nitrogen and theoxygen and moisture concentration is maintained to be less than 1 ppm.Since the mineralizers are reactive with oxygen and moisture, themineralizers are stored in the glove box at all times. 2.4 g of Na wasused as a mineralizer. As explained in Example 6, Na was melted in Nicrucible, capped with Ni foil and solidified. 0.1 g of Mg was added inthe Ni crucible on top of the Ni foil. After loading the Ni crucibleinto the high-pressure vessel, six baffles together with seeds andnutrient were loaded. After sealing the high-pressure vessel, it wastaken out of the glove box. The high-pressure vessel was connected to agas/vacuum system, which can pump down the vessel as well as supply NH₃to the vessel. The high-pressure vessel was evacuated with a turbomolecular pump to achieve pressure less than 1×10⁻⁵ mbar. The actualpressure before filling ammonia was 1.4×10⁻⁷ mbar. In this way, residualoxygen and moisture on the inner wall of the high-pressure vessel wereremoved. After this, the high-pressure vessel was chilled with liquidnitrogen and NH₃ was condensed in the high-pressure vessel.Approximately 40 g of NH₃ was charged in the high-pressure vessel. Afterclosing the high-pressure valve of the high-pressure vessel, it wastransferred to a two zone furnace. The high-pressure vessel was heatedup. For the first 24 hours, only the furnace for the nutrient region wasturned on and maintained at 550° C. while maintaining the furnace forthe crystallization region off in order to back etch the surface of theseed. This reverse temperature setting was discovered to be beneficialfor improving crystal quality as shown in Example 15. Then, thetemperatures for the crystallization region and the nutrient region wereset to 590 and 575° C. for growth. After 9 days, ammonia was releasedand the high-pressure vessel was opened. The grown crystal showed almosttransparent as shown in FIG. 3. Thus, reducing oxygen contamination inthe process is very effective to improve transparency of the crystal.

Example 13

Seed crystals are usually prepared by slicing bulk GaN with wire sawfollowed by polishing. There is a damage layer at the surface of theseeds created by these slicing and polishing process. To improvestructural quality of GaN, it is necessary to remove this damage layer.In addition, impurities physically or chemically adsorbed on the seedsurface can be removed with back etching. In this example, ahigh-pressure vessel having an inner diameter of 1 inch was used todemonstrate the back etching of the seed in the ammonothermalhigh-pressure vessel. Unlike the Examples 1, 2, this high-pressurevessel has an open end on one side. A GaN seed crystal was back etchedby setting the temperature of the crystallization region lower than thatof the nutrient region. All necessary sources and internal componentsincluding 10 g of polycrystalline GaN nutrient held in a Ni basket, one0.4 mm-thick single crystalline GaN seed, and six flow-restrictingbaffles were loaded into a glove box together with the high-pressurevessel. The glove box is filled with nitrogen and the oxygen andmoisture concentration is maintained to be less than 1 ppm. Since themineralizers are reactive with oxygen and moisture, the mineralizers arestored in the glove box at all times. 4 g of NaNH₂ was used as amineralizer. After loading the mineralizer into the high-pressurevessel, six baffles together with the seed and nutrient were loaded.After sealing the high-pressure vessel, it was taken out of the glovebox. Then, the high-pressure vessel was connected to a gas/vacuumsystem, which can pump down the vessel as well as supply NH₃ to thevessel. The high-pressure vessel was heated at 125° C. and evacuatedwith a turbo molecular pump to achieve pressure less than 1×10⁻⁵ mbar.The actual pressure before filling ammonia was 1.8×10⁻⁶ mbar. In thisway, residual oxygen and moisture on the inner wall of the high-pressurevessel were removed. After this, the high-pressure vessel was chilledwith liquid nitrogen and NH₃ was condensed in the high-pressure vessel.Approximately 40 g of NH₃ was charged in the high-pressure vessel. Afterclosing the high-pressure valve of the high-pressure vessel, it wastransferred to a two zone furnace. The high-pressure vessel was heatedup. The furnace for the crystallization region was maintained off andthe nutrient region was maintained at 550° C. The actual temperaturemeasured in the crystallization region was 366° C. It is very importantto maintain the temperature difference more than 50° C. to avoid GaNdeposition on the seed due to concentration gradient. After 24 hours,ammonia was released and the high-pressure vessel was opened. The seedcrystal was back etched by 36 microns, which is sufficient to removedamage layer created by slicing and polishing.

Example 13

Although GaN has retrograde solubility at temperatures higher thanapproximately 400° C., the solubility has normal (i.e. positive)dependence on temperature below approximately 400° C. Therefore it ispossible to back etch the seed crystals by setting the crystallizationzone lower than 400° C. and maintaining the temperature ofcrystallization zone higher than that of other zones. It is important tomaintain the temperature of the nutrient region at least 50° C. lowerthan the crystallization region to avoid GaN deposition on the seed dueto concentration gradient.

Example 14

Seed crystals are usually prepared by slicing bulk GaN with wire sawfollowed by polishing. There is a damage layer at the surface of theseeds created by these slicing and polishing process. To improvestructural quality of GaN, it is necessary to remove this damage layer.In addition, impurities physically or chemically adsorbed on the seedsurface can be removed by back etching. In this example, seed crystalswere back etched in a separate reactor prior to the ammonothermalgrowth. Seed crystals with thickness of approximately 0.4 mm were loadedin a furnace reactor which can flow ammonia, hydrogen chloride, hydrogenand nitrogen. In this example, seed crystals were etched in mixture ofhydrogen chloride, hydrogen and nitrogen. The flow rate of hydrogenchloride, hydrogen and nitrogen was 25 sccm, 60 sccm, and 1.44 slm,respectively. The etching rate was 7, 21, 35, and 104 microns/h for 800,985, 1000, 1050° C. Therefore, back etching above 800° C. givessufficient removal of the surface layer.

Example 15

We discovered that structural quality of grown crystals was improved byutilizing reverse temperature condition during initial temperature ramp.In this example, a high-pressure vessel having an inner diameter of 1inch was used to demonstrate the effect of reverse temperature settingin the initial stage of growth. Unlike the Examples 1, 2, thishigh-pressure vessel has an open end on one side. All necessary sourcesand internal components including 10 g of polycrystalline GaN nutrientheld in a Ni basket, 0.4 mm-thick single crystalline GaN seeds, andthree flow-restricting baffles were loaded into a glove box togetherwith the high-pressure vessel. The glove box is filled with nitrogen andthe oxygen and moisture concentration is maintained to be less than 1ppm. Since the mineralizers are reactive with oxygen and moisture, themineralizers are stored in the glove box at all times. 4 g of NaNH₂ wasused as a mineralizer. After loading the mineralizer into thehigh-pressure vessel, three baffles together with seeds and nutrientwere loaded. After sealing the high-pressure vessel, it was taken out ofthe glove box. Then, the high-pressure vessel was connected to agas/vacuum system, which can pump down the vessel as well as supply NH₃to the vessel. The high-pressure vessel was heated at 120° C. andevacuated with a turbo molecular pump to achieve pressure less than1×10⁻⁵ mbar. The actual pressure before filling ammonia was 1.5×10⁻⁶mbar. In this way, residual oxygen and moisture on the inner wall of thehigh-pressure vessel were removed. After this, the high-pressure vesselwas chilled with liquid nitrogen and NH₃ was condensed in thehigh-pressure vessel. Approximately 40 g of NH₃ was charged in thehigh-pressure vessel. After closing the high-pressure valve of thehigh-pressure vessel, it was transferred to a two zone furnace andheated up. The furnace for the crystallization region was maintained at510° C. and the nutrient region was maintained at 550° C. for 6 hours.Then, the temperatures for the crystallization region and the nutrientregion were set to 575 and 510° C. for growth. After 7 days, ammonia wasreleased and the high-pressure vessel was opened. The grown crystals hadthickness of approximately 1 mm. The structural quality was improvedcompared to one with conventional ammonothermal growth [5]. The fullwidth half maximum (FWHM) of X-ray rocking curve from (002) and (201)planes were 169 and 86 arcsec, respectively.

Example 16

We discovered that setting the crystallization temperature slightlylower than the nutrient temperature during growth significantly reducedparasitic deposition of polycrystalline GaN on the inner surface ofreactor. Although the GaN has retrograde solubility in supercriticalammonobasic solution as disclosed in the Ref. [6, 13-16], we discoveredthat GaN crystal growth occurred even with reverse temperaturecondition. Moreover, structural quality of grown crystal was improvedwithout sacrificing growth rate.

A high-pressure vessel having an inner diameter of 1 inch was used todemonstrate the effect of reverse temperature setting during growth.Unlike the Examples 1, 2, this high-pressure vessel has an open end onone side. All necessary sources and internal components including 10 gof polycrystalline GaN nutrient held in a Ni basket, 0.47 mm-thicksingle crystalline GaN seeds, and six flow-restricting baffles wereloaded into a glove box together with the high-pressure vessel. Theglove box is filled with nitrogen and the oxygen and moistureconcentration is maintained to be less than 1 ppm. Since themineralizers are reactive with oxygen and moisture, the mineralizers arestored in the glove box at all times. 2.6 g of Na solidified in Nicrucible and capped with Ni foil as explained in Example 6 was used as amineralizer. After loading the Ni crucible into the high-pressurevessel, six baffles together with seeds and nutrient basket were loaded.After sealing the high-pressure vessel, it was taken out of the glovebox. Then, the high-pressure vessel was connected to a gas/vacuumsystem, which can pump down the vessel as well as supply NH₃ to thevessel. The high-pressure vessel was and evacuated with a turbomolecular pump to achieve pressure less than 1×10⁻⁵ mbar. The actualpressure before filling ammonia was 9.5×10⁻⁸ mbar. In this way, residualoxygen and moisture on the inner wall of the high-pressure vessel wereremoved. After this, the high-pressure vessel was chilled with liquidnitrogen and NH₃ was condensed in the high-pressure vessel.Approximately 44 g of NH₃ was charged in the high-pressure vessel. Afterclosing the high-pressure valve of the high-pressure vessel, it wastransferred to a two zone furnace and heated up. For the first 24 hours,the furnace for the crystallization zone and nutrient zone were rampedand maintained at 360° C. and 570° C., respectively. As explained inExample 15, this reverse temperature setting ensures back etching of theseed. Then, the crystallization zone was heated and maintained to 535°C. in about 10 minutes and the nutrient region was cooled from 570° C.down to 540° C. in 24 hours. The slow cooling of the nutrient region isexpected to reduce sudden precipitation of GaN in the initial stage ofgrowth. After the temperature of the nutrient region became 540° C.,this reverse temperature setting (i.e. 535° C. for crystallizationregion and 540° C. for nutrient region) was maintained for 3 more days.Then, the ammonia was released, reactor was unsealed and cooled. Thegrown crystals had thickness of approximately 1.2 mm. The average growthrate was 0.183 mm/day. The structural quality was improved compared toone with conventional ammonothermal growth [5]. The full width halfmaximum (FWHM) of X-ray rocking curve from (002) and (201) planes were56 and 153 arcsec, respectively. Also, parasitic deposition was about0.3 g, which was more than 50% reduced compared to the conventionaltemperature setting.

Advantages and Improvements

The disclosed improvements enable mass production of high-quality GaNwafers via ammonothermal growth. By utilizing the new high-pressurevessel design, one can maximize the high-pressure vessel with sizelimitation of available Ni—Cr based precipitation hardenable superalloy.Procedures to reduce oxygen contamination in the growth system ensureshigh-purity GaN wafers. Small amount of additives such as Ce, Ca, Mg,Al, Mn, Fe, B, In, Zn, Sn, Bi helps to improve crystal quality. In-situor ex-situ back etching of seed crystals is effective way to removedamaged layer and any adsorbed impurities from GaN seeds. In addition,reverse temperature setting even for growth scheme is beneficial forreducing parasitic deposition of polycrystalline GaN on the innersurface of the reactor and improving structural quality. Thesetechniques help to improve quality of group III nitride crystals andwafers.

Possible Modifications

Although the preferred embodiment describes a two-zone heater, theheating zone can be divided into more than two in order to attainfavorable temperature profile.

Although the preferred embodiment describes the growth of GaN as anexample, other group III-nitride crystals may be used in the presentinvention. The group III-nitride materials may include at least one ofthe group III elements B, Al, Ga, and In.

Although the preferred embodiment describes the use of polycrystallineGaN nutrient, other form of source such as metallic Ga, amorphous GaN,gallium amide, gallium imide may be used in the present invention.

In the preferred embodiment specific growth apparatuses are presented.However, other constructions or designs that fulfill the conditionsdescribed herein will have the same benefit as these examples.

Although the example in the preferred embodiment explains the processstep in which NH₃ is released at elevated temperature, NH₃ can also bereleased after the high-pressure vessel is cooled as long as seizing ofscrews does not occur.

The foregoing description of the preferred embodiment of the inventionhas been presented for the purposes of illustration and description. Itis not intended to be exhaustive or to limit the invention to theprecise form disclosed. Many modifications and variations are possiblein light of the above teaching. It is intended that the scope of theinvention be limited not by this detailed description, but rather by theclaims appended hereto.

REFERENCES

The following references are incorporated by reference herein:

-   [1]. S. Porowski, MRS Internet Journal of Nitride Semiconductor,    Res. 4S1, (1999) G1.3.-   [2] T. Inoue, Y. Seki, O. Oda, S. Kurai, Y. Yamada, and T. Taguchi,    Phys. Stat. Sol. (b), 223 (2001) p. 15.-   [3] M. Aoki, H. Yamane, M. Shimada, S. Sarayama, and F. J.    DiSalvo, J. Cryst. Growth 242 (2002) p. 70.-   [4] T. Iwahashi, F. Kawamura, M. Morishita, Y. Kai, M. Yoshimura, Y.    Mori, and T. Sasaki, J. Cryst Growth 253 (2003) p. 1.-   [5] T. Hashimoto, F. Wu, J. S. Speck, S, Nakamura, Jpn. J. Appl.    Phys. 46 (2007) L889.-   [6] R. Dwiliński, R. Doradziński, J. Garczyński, L.    Sierzputowski, Y. Kanbara, U.S. Pat. No. 6,656,615.-   [7] R. Dwiliński, R. Doradziński, J. Garczyński, L.    Sierzputowski, Y. Kanbara, U.S. Pat. No. 7,132,730.-   [8] R. Dwiliński, R. Doradziński, J. Garczyński, L.    Sierzputowski, Y. Kanbara, U.S. Pat. No. 7,160,388.-   [9] K. Fujito, T. Hashimoto, S, Nakamura, International Patent    Application No. PCT/US2005/024239, WO07008198.-   [10] T. Hashimoto, M. Saito, S, Nakamura, International Patent    Application No. PCT/US2007/008743, WO07117689. See also    US20070234946, U.S. application Ser. No. 11/784,339 filed Apr. 6,    2007.-   [11] S. Kawabata, A. Yoshikawa, JP 2007-290921.-   [12] M. P. D'Evelyn, K. J. Narang, U.S. Pat. No. 6,398,867 B1.-   [13] D. Peters, J. Cryst. Crowth, 104 (1990) 411.-   [14] T. Hashimoto, K. Fujito, B. A. Haskell, P. T. Fini, J. S.    Speck, and S, Nakamura, J. Cryst. Growth 275 (2005) e525.-   [15] M. Callahan, B. G. Wang, K. Rakes, D. Bliss, L.    Bouthillette, M. Suscavage, S. Q. Wang, J. Mater. Sci. 41 (2006)    1399.-   [16] T. Hashimoto, M. Saito, K. Fujito, F. Wu, J. S. Speck, S,    Nakamura, J. Cryst. Growth 305 (2007) 311.

Each of the references above is incorporated by reference in itsentirety as if put forth in full herein, and particularly with respectto description of methods of making using ammonothermal methods andusing these gallium nitride substrates.

What is claimed is:
 1. An article comprising a. a mineralizer comprising an element that aids in ammonothermal growth of a group III-nitride crystal in a high-pressure reactor; and b. a covering upon the mineralizer that prevents oxygen from contaminating the mineralizer, said covering being compatible with the ammonothermal growth of the group III-nitride crystal.
 2. An article according to claim 1 wherein the mineralizer comprises an alkali metal mineralizer.
 3. An article according to claim 2 wherein the alkali metal mineralizer comprises at least one of Na, Li, and K.
 4. An article according to claim 2 wherein the covering encapsulates the mineralizer and is oxygen- and water-impermeable.
 5. An article according to claim 2 wherein the covering releases the mineralizer while the high-pressure vessel is self-pressurized by heating.
 6. An article according to claim 1 wherein the mineralizer comprises Na.
 7. An article according to claim 6 wherein the mineralizer comprises NaNH₂.
 8. An article according to claim 6 wherein the mineralizer comprises elemental Na.
 9. An article according to claim 1 wherein the covering comprises a metal layer.
 10. An article according to claim 9 wherein the metal layer comprises a metal foil.
 11. An article according to claim 9 wherein the metal layer encapsulates the mineralizer.
 12. An article according to claim 9 wherein the metal comprises nickel.
 13. An article according to claim 1 wherein the covering comprises a container.
 14. An article according to claim 13 wherein the article was formed by a method of pouring molten mineralizer into the container and solidifying the molten mineralizer.
 15. An article according to claim 14 wherein a top surface of the mineralizer is covered with a foil.
 16. An article according to claim 13 wherein the container has a yield strength that is exceeded at group III-nitride crystal ammonothermal growth conditions.
 17. An article according to claim 13 wherein the container ruptures as the high-pressure reactor attains conditions for ammonothermal growth of the group III-nitride crystal.
 18. An article according to claim 1 and additionally comprising an oxygen getter accompanying the mineralizer.
 19. An article according to claim 1 wherein the covering encapsulates the mineralizer and is oxygen- and water-impermeable.
 20. An article according to claim 1 wherein the covering releases the mineralizer while the high-pressure vessel is self-pressurized by heating.
 21. An article according to claim 1 wherein the covering comprises a metal which is stable in supercritical ammonia. 